Certain fluoro-dichloromethyldithiobenzazole compounds



United States Patent F 5, Claims. (Cl.260306.5)

In US. application Serial No. 148,845, filed October 31, 1961, sulphenic acid derivatives of the general formula are described which are obtained by reacting corresponding imino-compounds with dichloro-fluoro-methane sulphenic acid chloride.

In the aforesaid formula Y and Z represent CO- and/ or SO -groups which are further linked with a similar or different organic radical, an optionally substituted amino group or a common organic radical (with ring coupling); Z can also stand for an organic radical which is linked to the nitrogen optionally via another hetero atom.

The aforesaid compounds show a quite remarkable fungicidal activity at a relatively good plant tolerance.

It has now been found that insecticidal and acaricidal and partly also fungicidal derivativesof fluoro-dichloromethane sulphenic acid are obtained if fluoro-dichloromethane sulphenic acid chloride is caused to react with compounds of the general formula RX-H according to the following reaction scheme:

RXH+ClSCFCl RX-SCFC1 In the formula R stands for an optionally substituted aliphatic radical, an alkoxy alkyl radical, an alkyl-thio radical as well as for a radical in which R" stands for an alkyl radical, an alkylthio radical and an amino group and Y stands for sulfur or a NR' radical.

R further stands for a cycloaliphatic, aromatic and heterocyclic radical. X stands for oxygen, sulfur and the N-R' radical where R stands for hydrogen, an aliphatic, cycloaliphatic or aromatic radical and NR taken together with R stands for a 5 to 6 membered heterocyclic ring system.

If R represents an aliphatic radical it preferably stands for an aliphatic radical containing 1 to 12 carbon atoms. This radical may be substituted by halogen. If R represents an aromatic radical this radical may further be substituted by halogen or the nitro group. If R represents a heterocyclic radical this radical may also contain an aromatic radical adjacent to the heterocyclic radical.

Suitable starting compounds for this process are aliphatic, aromatic or heterocyclic alcohols and mercaptans, phenols, dithiocarbamic acid salts, xanth-ic acid salts, primary and secondary amines and the like. The above-mentioned reaction is expediently carried out at room temperature and in an inert solvent in the presence of an acid-binding agent; in most cases the reaction leads to the desired result in aqueous phase with alkali metal or alkaline earth metal salts of the compounds concerned.

and 22 g. of thiophenol in 100 m1. of benzene.

"ice

Finally the starting compounds can also be reacted with fluoro-dichloroamethane sulphenic acid chloride With- Example 1 15.2 g. of ethylene glycol monomethyl ether are dissolved in 200 ml. of benzene with addition of 22 g. of tri ethylamine and mixed with 34 g. of fluoro-dichloro-met-hane sulphenic acid chloride at room temperature. The temperature rises to about 50 C. The amine salt is filtered off with suction, the solution is concentrated in vacuum and the fluoro-dichloro-methane sulphenic acid- (2-methoxy-ethyl ester), distilled, which boils at 72-76 C. at 10 mm. Hg. Yield: 23 g.

This compound kills flies to the extent of 100% in an applied amount of 0.2%.

In the same way the following esters are produced:

Drosophila Mites CHsOSCFClz ClOHzCHzOSCFClz moiosoroig mohoosorol uu HgaCmOSCFCls mm. Hg. 74-78 C./12

mm. Hg. 63-68 C./10

nun. Hg. 52-55" C./10

mm. Hg. 170180 C./12

mm. Hg.

Example 2 19 g. of phenol and 34 g. of fluoro-dichloro-methane sulphenic acid chloride are dissolved in 100 in]. of benzene and treated dropwise with 21 g. of trie-thylamine. The temperature rises to about 50 C. It is stirred, filtered off with suction from the amine salt and distilled after removal of the solvent in vacuum. 25 g. of fiuoro-dichlorm methane sulphenic acid phenyl ester of B.P. 93l00 C. at 12 mm. Hg, are thus obtained which possesses a 100% activity against flies at 0.2% application.

In an analogous manner there are obtained:

21 g. of triethylamine are added dropwise to a solution of 34 g. fluoro-dichloro-methane sulphenic acid chloride The temperature thereby rises to about 40 C. After the usual working up 43 g. of fluoro-diohloro-methane-sulphenic acid thiophenyl ester of B.P. 127130 C. at 13 mm. Hg are obtained by vacuum distillation, which on application in amounts of 0.2% kills caterpillars to 100% and at 0.02% still possesses a 100% effect against flies.

Percent killed at 0.2%

In an analogous manner fl'uoro-dichloro-methane sulphenic acid thiododecyl ester is obtained which kills mites at 0.2% application.

. Example 4 4 We claim: 1. A compound of the formula 23 of Z-mercapto-benzoxazole are dissolved in 200 5 wherein R i s amember selected from the t a group conslstln Water Wlth addltlo? of of sodlun} hydroxlde and of benzoxazolyl, and monochloro-benzoxazolyl; and X i: mlxed at l5-20 C. with 26 g. of fluoro-dichloro-methane a lf atom sulphenic acid chloride. g. of benzoxazolyl-fiuoro-di- A compound of the formula chloro-methyl disulphide are thus obtained as an oily product. The compound kills flies at a concentration of 10 r I 0.2% to the extent of 100%.

In an analogous manner the following disulphides are obtained: wherein R is benzthiazolyl and X is a sulfur atom.

Percent killed at 0.2% B.P.

Caterpillars Drosophila Mites N 01 10o C Z v 100 /SSCI-C12 Q :o 169-l72C./11mm.Hg ,100

OOHa Percent killed at 0.2% B.P.

Caterpillars Drosophila Mites N Q N -sso1 c1 Oily 100 100 100 CSSCFCIZ M.P. 60-63"- 100 100 s (oHmNfiJssoFon Oily 100 HsCgOOQSCFClg 124-129 0.113 mm. Hg 100 100 70 Example 3. A compound having the formula A solution of 34 g. of fiuoro-dichloro-methane sulphenic acid chloride in 100 ml. of benzene is treated drop- H wise at room temperature with a solution of 34 g. of piper- C 830F012 idene in 50 m1. of benzene. After removal of the amine salt there are obtained by vacuum distillation 29 g. of fiuoro-dichloro-methane sulphenic acid piperidide of BR 4. A compound having the formula Sit-89 C. at 11 mm. Hg, which kills flies to the extent of 100% at 0.2% application. N

In an analogous maner there are obtained: 01

. OSSOFCI:

Percent killed 0 13.1. at 0.02% DmSOphfia 5. A compound having the formula @N-SGFG1 120-127o /11 mm Hg 100 N l I 0 l Q CSSCFOI: N-SCFClg Oily 100 (References on following page) References Cited by the Examiner UNITED STATES PATENTS 2,553,777 5/1951 Hawley et a1. 260-3065 2,862,946 12/1958 Kharasch 260456 5 FOREIGN PATENTS 1,241,754 8/ 1960 France.

6 OTHER REFERENCES Frear et al., J. Ecen. Entomology, vol. 40, pp. 736- 741 (1947). I

Sheppard et al., J. Chem. Soc., vol. 82, pp.-5106-7 (1960).

NICHOLAS S. RIZZO, Primary Examiner.

ALTON D. ROLLINS, Assistant Examiner. 

1. A COMPOUND OF THE FORMULA 